Skin care cosmetic compositions containing carboxymethylates of branched alcohols and/or ethoxylates thereof

ABSTRACT

Cosmetic skin care methods and compositions containing carboxymethylates of branched alcohols and/or ethoxylates thereof. The inventive compositions provide control of sebum secretion from sebocytes, improved oil control and improved skin feel, prevent shine and stickiness, while also providing anti-aging benefits which results in reduced appearance of wrinkles and aged skin, improved skin color, treatment of photoaged skin, improvement in skin&#39;s radiance and clarity and finish, and an overall healthy and youthful appearance of the skin.

This application claims benefit of U.S. Provisional Application No.60/215,573 under 35 U.S.C. 119(e), filed Jun. 30, 2000.

FIELD OF THE INVENTION

Cosmetic methods and compositions for conditioning human skin by topicalapplication to the skin of cosmetic compositions containingcarboxymethylates of branched alcohols, and/or ethoxylates thereof.

BACKGROUND OF THE INVENTION

Sebum is skin oil which is produced by sebocytes (cells of the sebaceousglands in the skin) and is then secreted to the skin surface. A frequentand undesirable skin condition is “oily skin,” the condition whichresults from the excessive amount of sebum on the skin. Oily skin isassociated with a shiny, undesirable appearance and a disagreeabletactile sensation and affects various age groups. Therefore, cosmeticproducts which provide both sebum control and anti-aging benefits arehighly desirable.

The prior art discloses branched alcohols as compounds which provideskin benefits such as sebum suppression. For example, U.S. Pat. No.5,756,109 issued to Burger et al. (hereinafter “Burger '109”) teachesthe use of a noncylic polyunsaturated diterpene alcohol, geranylgeraniol, in combination with a retinol as a skin conditioningcomposition. Burger '109 discloses sebum suppression as one advantage ofthe branched alcohol in combination with retinol. U.S. Pat. No.5,344,850 issued to Hata et al. discloses topical compositionscontaining C₁₈ saturated or unsaturated alcohol with four methylbranches for treating or preventing acne.

A problem exists in that branched alcohols alone inherently possess anunpleasant odor, characteristic of vinyl or a “new car smell,” makingapplication in cosmetic skin conditioning compositions highlyundesirable. Moreover, branched alcohols themselves are water-insoluble.

Derivatives of branched alcohols have also been disclosed in the priorart for a variety of uses, such as personal cleansing compositions. Forexample, WO 9918928 assigned to The Proctor & Gamble Company, disclosespersonal cleansing compositions comprising branched surfactant systemshaving a hydrophobic group and a hydrophilic group. The hydrophobicgroup comprises mid-chain branched and linear surfactant compounds. Thehydrophilic group is selected from the group consisting of sulfateand/or ethoxylates thereof.

U.S. Pat. No. 3,992,443 issued to Springmann (hereinafter “Springmann'443”) discloses a process for the carboxymethylation of alcohols orether alcohols in a single stage. Springmann '443 teaches the use ofboth straight chain and branched alcohols as suitable starting alcohols.

U.S. Pat. No. 6,020,303 issued to Cripe et al. (hereinafter “Cripe'303”) discloses detergent surfactant compositions derived frommid-chain branched primary alkyl hydrophobic groups and hydrophilicgroups. Specifically, Cripe '303 discloses alkyl sulfates forapplication in laundry and cleaning compositions.

U.S. Pat. No. 5,093,112 issued to Birtwistle et al. discloses topicalcleansing (detergent) compositions containing an alcohol and an alkyl oralkenyl phosphate salt.

The prior art cited above does not seem to suggest or disclose cosmeticcompositions or methods for skin conditioning which avoid the negativecharacteristics of branched alcohols. Therefore, a need remains forcosmetic compositions that retain the beneficial effects of branchedalcohols in relation to sebum suppression and skin conditioning whileavoiding the unpleasant odor and water-insolubility associated with suchalcohols.

SUMMARY OF THE INVENTION

The present invention includes a skin care cosmetic compositioncomprising:

(i) from about 0.001% to about 50% of a compound of the formula A:

R—O—M  (A)

 wherein:

R is a branched alkyl chain having at least 9 carbon atoms, generallyfrom 9 to 15 atoms, and at least two branches;

O is an oxygen atom; and

M is (—CH₂CO₂X) or (—(CH₂CH₂O)_(n)—CH₂CO₂X) and mixtures thereof, wheren is an integer of at least 1 and X is hydrogen or a cation; and

(ii) a cosmetically acceptable vehicle.

The present invention also includes a cosmetic method of controlling orpreventing an oily skin condition, especially in the facial area, byapplying to the skin the inventive composition.

The invention also includes a cosmetic method of reducing, preventing orcontrolling sebum secretion from sebocytes by applying the inventivecomposition.

The invention also includes a cosmetic method of stimulating collagensynthesis by fibroblasts in the skin, by applying to the skin theinventive composition. The inventive methods and compositions providecontrol of sebum secretion from sebocytes, improved oil control andimproved skin feel, and prevent shine and stickiness, while alsoproviding anti-aging benefits which results in reduced appearance ofwrinkles and aged skin, improved skin color, treatment of photoagedskin, improvement in skin's radiance and clarity and finish, and anoverall healthy and youthful appearance of the skin.

DETAILED DESCRIPTION OF THE INVENTION

Except in the operating and comparative examples, or where otherwiseexplicitly indicated, all numbers in this description indicating amountsof material or conditions of reaction, physical properties of materialsand/or use are to be understood as modified by the word “about.” Allamounts are by weight of the oil-in-water emulsion, unless otherwisespecified.

The term “skin” as used herein includes the skin on the face, neck,chest, back, arms, hands, legs and scalp.

The inventive methods and compositions include a carboxymethylate of abranched alcohol, and/or ethoxylates thereof (hereinafter “compound A”),and are of the general formula A:

R—O—M  (A)

wherein:

R is a branched alkyl chain having at least 9 carbon atoms, generallyfrom 9 to 15 atoms, and at least two branches;

O is an oxygen atom; and

M is (—CH₂CO₂X) or (—(CH₂CH₂O)_(n)—CH₂CO₂X) and mixtures thereof,

where n is an integer of at least 1 and X is hydrogen or a cation. Thecation may be selected from the group consisting of sodium, lithium,potassium, calcium, magnesium, manganese and amines including quartenaryalkyl amines, but is not limited thereto.

The branched alkyl chain of the present invention is derived from abranched alcohol having at least 9 carbon atoms and at least twobranches, as noted above. As seen in Example 1 discussed infra, alcoholswith less than 9 carbons do not aid in collagen synthesis. The preferredalcohols from which the inventive compositions are derived contain atotal of at least 10 carbon atoms in order to obtain maximum efficacy.The most preferred alcohols from which the inventive compositions arederived, contain from 2 to 5 branches, in order to maximize efficacy atminimum cost. Preferably, the branches are methyl branches, due tocommercial availability. The alcohol may contain a mix of various chainlengths' alcohols. Such mixed alcohol is suitable in deriving theinventive compositions, as long as the predominant alcohol in the mixcontains a total of at least 9 carbon atoms and at least two branches.

Carboxymethylation of the branched alcohol involves the addition of acarboxyl group to the branched alcohol. Compound A is derived fromalcohols which are commercially available, e.g. from Exxon or Henkel.Ethoxylation involves first directly adding an ethylene oxide to thebranched alcohol, followed by carboxymethylation.

The salt forms of compound A (where M is a cation in formula A) arepreferred because they provide a neutral pH for the inventivecompositions before application to the skin to avoid irritation.Moreover, the salts dissociate upon contact with the skin to release thebeneficial characteristics of the anionic nature of the inventivecompositions. Preferably, sodium salt is used because of commercialavailability.

Compound A of the present invention retains the beneficial sebumsuppression qualities of branched alcohols while eliminating theunpleasant odor. Moreover, compound A is an anionic surfactant, thusproviding a negative charge that aids in binding the surfactant onto theskin's surface. The water soluble characteristic effectuates deliveryinto the skin. Moreover, as compared to prior art surfactants such assulfate groups on branched alcohols, the carboxyl group in compound A isa better metal chelator and milder to the skin due to its relatively lowacidity (pKa of approximately 3). The carboxyl group has a lowermolecular weight than a sulfate group, thus lower amounts of thecarboxyl group will yield more beneficial results than the sulfategroup.

Compound A is employed in the inventive methods and compositions in anamount of from 0.001% to about 50%, preferably from 0.1% to 20%, mostpreferably from 0.1% to 10%.

The inventive compositions containing compound A may also include aretinoid. Retinoids increase collagen synthesis by dermal fibroblasts.This results in protection from sun damage and smoothening of wrinkledskin. Addition of retinoids to compound A provided improved inhibitionof lipogenesis as well as increased collagen synthesis in comparison tocompound A alone. The term “retinoids” as used herein includes retinoicacid, retinol, retinal, and retinyl esters. Included in the term“retinoic acid” are 13-cis retinoic acid and all-trans retinoic acid.

The term “retinol” as used herein includes the following isomers ofretinol: all-trans-retinol, 13-cis-retinol, 11-cis-retinol,9-cis-retinol, 3,4-didehydro-retinol. Preferred isomers areall-trans-retinol, 13-cis-retinol, 3,4-didehydro-retinol, 9-cis-retinol,9-cis-retinol. Most preferred is all-trans-retinol, due to its widecommercial activity.

Retinyl ester is an ester of retinol. The term “retinol” has beendefined above. Retinyl esters suitable for use in the present inventionare C₁-C₃₀ esters of retinol, preferably C₂-C₂₀ esters, and mostpreferably C₂, C₃, and C₆ esters because they are more commonlyavailable. Examples of retinyl esters include but are not limited to:retinyl palmitate, retinyl formate, retinyl acetate, retinyl propionate,retinyl butyrate, retinyl valerate, retinyl isovalerate, retinylhexanoate, retinyl heptanoate, retinyl octanoate, retinyl nonanoate,retinyl decanoate, retinyl undecandate, retinyl laurate, retinyltridecanoate, retinyl myristate, retinyl pentadecanoate, retinylheptadeconoate, retinyl stearate, retinyl isostearate, retinylnonadecanoate, retinyl arachidonate, retinyl behenate, retinyllinoleate, retinyl oleate, retinyl lactate, retinyl glycolate, retinylhydroxy caprylate, retinyl hydroxy laurate, retinyl tartarate.

The retinoids in the present invention are present in an amount of from0.001% to 10%, preferably from 0.01% to 1%, and most preferably from0.01% to 0.05%.

Compound A employed in the inventive methods and compositions is liquid,and thus the invention is effective even in the absence of the carrier.However, the compositions according to the invention comprise acosmetically acceptable vehicle to act as a diluant, dispersant orcarrier of compound A thereof, so as to facilitate their distributionwhen the composition is applied to the skin.

The vehicle may be aqueous, anhydrous or an emulsion. Preferably, thecompositions are aqueous or an emulsion, especially water-in-oil oroil-in-water emulsion. Water when present will be in amounts which mayrange from 5 to 99%, preferably from 40 to 90%, optimally between 60 and90% by weight.

Besides water, relatively volatile solvents may also serve as carrierswithin compositions of the present invention. Most preferred aremonohydric C₁-C₃ alkanols. These include ethyl alcohol, methyl alcoholand isopropyl alcohol. The amount of monohydric alkanol may range from 1to 70%, preferably from 10 to 50%, optimally between 15 and 40% byweight.

Emollient materials may also serve as cosmetically acceptable carriers.These may be in the form of silicone oils and synthetic esters. Amountsof the emollients may range anywhere from 0.1 to 50%, preferably between1 and 20% by weight.

Silicone oils may be divided into the volatile and non-volatile variety.The term “volatile” as used herein refers to those materials which havea measurable vapor pressure at ambient temperature. Volatile siliconeoils are preferably chosen from cyclic or linear polydimethylsiloxanescontaining from 3 to 9, preferably from 4 to 5, silicon atoms. Linearvolatile silicone materials generally have viscosities less than about 5centistokes at 25° C. while cyclic materials typically have viscositiesof less than about 10 centistokes. Nonvolatile silicone oils useful asan emollient material include polyalkyl siloxanes, polyalkylarylsiloxanes and polyether siloxane copolymers. The essentiallynon-volatile polyalkyl siloxanes useful herein include, for example,polydimethyl siloxanes with viscosities of from about 5 to about 25million centistokes at 25° C. Among the preferred non-volatileemollients useful in the present compositions are the polydimethylsiloxanes having viscosities from about 10 to about 400 centistokes at25° C.

Among the ester emollients are:

(1) Alkenyl or alkyl esters of fatty acids having 10 to 20 carbon atoms.Examples thereof include isoarachidyl neopentanoate, isononylisonanonoate, oleyl myristate, oleyl stearate, and oleyl oleate.

(2) Ether-esters such as fatty acid esters of ethoxylated fattyalcohols.

(3) Polyhydric alcohol esters. Ethylene glycol mono and di-fatty acidesters, diethylene glycol mono- and di-fatty acid esters, polyethyleneglycol (200-6000) mono- and di-fatty acid esters, propylene glycol mono-and di-fatty acid esters, polypropylene glycol 2000 monooleate,polypropylene glycol 2000 monostearate, ethoxylated propylene glycolmonostearate, glyceryl mono- and di-fatty acid esters, polyglycerolpoly-fatty esters, ethoxylated glyceryl monostearate, 1,3-butyleneglycol monostearate, 1,3-butylene glycol distearate, polyoxyethylenepolyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylenesorbitan fatty acid esters are satisfactory polyhydric alcohol esters.

(4) Wax esters such as beeswax, spermaceti, myristyl myristate, stearylstearate and arachidyl behenate.

(5) Sterols esters, of which cholesterol fatty acid esters are examplesthereof.

Fatty acids having from 10 to 30 carbon atoms may also be included ascosmetically acceptable carriers for compositions of this invention.Illustrative of this category are pelargonic, lauric, myristic,palmitic, stearic, isostearic, hydroxystearic, oleic, linoleic,ricinoleic, arachidic, behenic and erucic acids.

Humectants of the polyhydric alcohol type may also be employed ascosmetically acceptable carriers in compositions of this invention. Thehumectant aids in increasing the effectiveness of the emollient, reducesscaling, stimulates removal of built-up scale and improves skin feel.Typical polyhydric alcohols include glycerol, polyalkylene glycols andmore preferably alkylene polyols and their derivatives, includingpropylene glycol, dipropylene glycol, polypropylene glycol, polyethyleneglycol and derivatives thereof, sorbitol, hydroxypropyl sorbitol,hexylene glycol, 1,3-butylene glycol, 1,2,6-hexanetriol, ethoxylatedglycerol, propoxylated glycerol and mixtures thereof. For best resultsthe humectant is preferably propylene glycol or sodium hyaluronate. Theamount of humectant may range anywhere from 0.5 to 30%, preferablybetween 1 and 15% by weight of the composition.

Thickeners may also be utilized as part of the cosmetically acceptablecarrier of compositions according to the present invention. Typicalthickeners include crosslinked acrylates (e.g. Carbopol 982),hydrophobically-modified acrylates (e.g. Carbopol 1382), cellulosicderivatives and natural gums. Among useful cellulosic derivatives aresodium carboxymethylcellulose, hydroxypropyl methylcellulose,hydroxypropyl cellulose, hydroxyethyl cellulose, ethyl cellulose andhydroxymethyl cellulose. Natural gums suitable for the present inventioninclude guar, xanthan, sclerotium, carrageenan, pectin and combinationsof these gums. Amounts of the thickener may range from 0.0001 to 5%,usually from 0.001 to 1%, optimally from 0.01 to 0.5% by weight.

Collectively, the water, solvents, silicones, esters, fatty acids,humectants and/or thickeners will constitute the cosmetically acceptablecarrier in amounts from 1 to 99.9%, preferably from 80 to 99% by weight.

An oil or oily material may be present, together with an emulsifier toprovide either a water-in-oil emulsion or an oil-in-water emulsion,depending largely on the average hydrophilic-lipophilic balance (HLB) ofthe emulsifier employed.

Various types of additional active ingredients may be present incosmetic compositions of the present invention. Actives are defined asskin benefit agents other than emollients and other than ingredientsthat merely improve the-physical characteristics of the composition.Although not limited to this category, general examples includeadditional anti-sebum ingredients such as talcs and silicas, andsunscreens.

Sunscreens include those materials commonly employed to blockultraviolet light. Illustrative compounds are the derivatives of PABA,cinnamate and salicylate. For example, avobenzophenone (Parsol 1789®)octyl methoxycinnamate and 2-hydroxy-4-methoxy benzophenone (also knownas oxybenzone) can be used. Octyl methoxycinnamate and2-hydroxy-4-methoxy benzophenone are commercially available under thetrademarks, Parsol MCX and Benzophenone-3, respectively. The exactamount of sunscreen employed in the compositions can vary depending uponthe degree of protection desired from the sun's UV radiation.

Many cosmetic compositions, especially those containing water, must beprotected against the growth of potentially harmful microorganisms.Preservatives are, therefore, necessary. Suitable preservatives includealkyl esters of p-hydroxybenzoic acid, hydantoin derivatives, propionatesalts, and a variety of quaternary ammonium compounds. Particularlypreferred preservatives of this invention are methyl paraben, propylparaben, phenoxyethanol and benzyl alcohol. Preservatives will usuallybe employed in amounts ranging from about 0.1% to 2% by weight of thecomposition.

The composition according to the invention is intended primarily as aproduct for No topical application to human skin, especially as an agentfor controlling or preventing excessive sebum secretion.

In use, a quantity of the composition, for example from 1 to 100 ml, isapplied to exposed areas of the skin, from a suitable container orapplicator and, if necessary, it is then spread over and/or rubbed intothe skin using the hand or fingers or a suitable device.

Product Form and Packaging:

The cosmetic skin composition of the invention can be in any form, e.g.formulated as a toner, gel, lotion, a fluid cream, or a cream. Thecomposition can be packaged in a suitable container to suit itsviscosity and intended use by the consumer. For example, a lotion orfluid cream can be packaged in a bottle or a roll-ball applicator or apropellant-driven aerosol device or a container fitted with a pumpsuitable for finger operation. When the composition is a cream, it cansimply be stored in a non-deformable bottle or squeeze container, suchas a tube or a lidded jar. The invention accordingly also provides aclosed container containing a cosmetically acceptable composition asherein defined.

The composition may also be included in capsules such as those describedin U.S. Pat. No. 5,063,057, incorporated by reference herein.

The following specific examples further illustrate the invention, butthe invention is not limited thereto.

The following alcohols used in the Examples were obtained from Exxon:

Trade Name Branching Exxal ® 7 Mixture of branched and straight chainisomers, about 40% dimethyl pentanols. Exxal ® 8 Methyl branching only,at least about 38% dimethyl hexanols. Exxal ® 10 Trimethyl heptanols anddimethyl octanols Exxal ® 12 Trimethyl nonanols Exxal ® 13 Tetramethylnonanols and trimethyl decanols

EXAMPLE 1

This example measured production of procollagen I by fibroblasts inresponse to treatment with various straight chain and branched alcoholsalone.

Collagen is a predominant skin protein. Its synthesis decreases withaging or photodamage. The degradation or destruction of collagenincreases the tensile strength of the skin causing wrinkles and laxity.Many studies involving human subjects have shown that collagen type I isdecreased with increasing severity of photodamage (See Kligman, A.,JAMA, (1969), 210, pp. 2377-2380; Lavker, R., J. Inv Derm., (1979), 73,79-66; Smith J. et al., J. Inv. Derm., (1962), 39, pp. 347-350; andShuster, S. et al., Br. J. Dermatol., (1975), 93, pp. 639-643); and somecorrelation in the histology of wrinkles and reduction in collagenlevels in the sun-exposed skin has been reported. See Chen, S.; Kiss,I., J. Inv. Derm., (1992), 98. pp. 248-254. Voorhees and colleagues havesupported these findings by showing the restoration of collagen type Iin photo-damaged human skin by a topical treatment with tretinoin. SeeChristopher, E., et al., The New Eng. Jou. of Medicine (1993), 329, pp.530-535. Procollagen I is a precursor of collagen. Increased productionof procollagen I in response to a test compound application is a markerof an increased collagen level.

Procollagen I Staining Protocol for Slot Blot

Neonatal human dermal fibroblasts were purchased from Clonetics Corp.,San Diego, Calif. All materials for cell culture were purchased fromLife Technologies, N.Y. (and used in passages 5-10). Cells were seededat a density of approximately 10,000/well in the inner 48 wells of a96-well plate in a medium containing DMEM (Dulbecco's Modified Eagle'sMedium), high-glucose supplemented with 2 mM L-glutamine, 10% fetalbovine serum, and antibiotic and antimycotic solutions. Cells were thengrown to confluence for 2 days. At confluence, the medium was removedand cells were washed with serum-free DMEM, and each well dosed with 200μl of a solution of a test compound in serum-free DMEM. Each dosing wasreplicated in a total of six wells. Test compounds were used atconcentrations indicated in Table 1 below. Control did not contain atest compound. After 24 hours, the test compound solution or the controlsolution was removed and cells redosed with 100 μl of a solution of atest compound in serum-free DMEM.

Nitrocellulose membrane and 3 sheets of filter paper were soaked in TRISbuffered saline (TBS, pH 7.3.). BioRad slot blot apparatus (BioRad Labs,CA) was set up with 3 sheets filter paper on bottom, membrane on top,and tightened. 100 ml TBS was added per well. Vacuum was used to suckTBS through membrane. The test compound solution or control wasvortexed, then 100 μl was loaded per well and gravity filtered.Procollagen from the test solution was bound to the membrane at thispoint in the procedure. Membrane was removed from the apparatus, excesscut off, and bottom right corner notched for orientation. The membranewas placed in blocking solution (5% milk powder in Dulbecco's phosphatebuffered saline) overnight at 4° C., with shaking. The membrane was thenincubated for 1.5 hrs at room temperature with 1.5 mL Rat Anti-HumanProcollagen Amino-Terminal Ab (Chemicon MAB1912) in TBS with 0.1% BSA(Bovine Serum Albumin) (ratio of antibody to buffer/BSA was 1:100) in asealed bag with shaking. The membrane was then removed; washed 3 timesfor 5 minutes in TBS/0.1% Tween. The membrane was then incubated for 1hour at room temperature in 2 mL of Biotinylated Anti-RatPeroxidase-Conjugated Ab (Vector Labs) in TBS with 0.1% BSA (ratio ofantibody to buffer/BSA was 1:1000) in a sealed bag with shaking. Themembrane was then stained using the following solution:

12.5 mg 3-amino 9-ethyl carbazole (Sigma)

3.125 (approximately) mL DMF (N,N-dimethylformamide, from Sigma)

21.5 mL 0.2M NaOAc buffer, pH 5.2

12.5 mL H₂O₂

The membrane was stained until color developed and the reaction stoppedwith 2 washes for 10 minutes in tap water. The blot was scanned on aBio-Rad GS700 Image Analysis densitometer. Percent change from controlwas calculated from densitometer readings as follows: [(Reading for testcompound-Reading for control)/Reading for control]*100. Control has areading of 100%. Statistical significance (p value) was calculated usingstudent's t-test.

The results that were obtained are summarized in Table 1. TGF-B is apositive control, ensuring the integrity of the assay: transforminggrowth factor beta is known to increase procollagen I in fibroblasts.

TABLE 1 % Increase (+) or % decrease (−) over Sample control Experiment1 TGF-B (transforming +50* growth factor-B) 0.01% Exxal ® 7 −10* 0.01%Exxal ® 8 −30* Experiment 2 TGF-B +140* 0.01% Exxal ® 10 +50* 0.01%Exxal ® 12 +40* 0.01% Exxal ® 13 +30* *statistically significant at p <0.05

It can be seen from the results in Table 1, that Exxal® 7 and Exxal® 8,which are not within the scope of the invention (i.e., at least a totalof 9 carbons in the branched alkyl chain with at least 2 branches), didnot increase collagen synthesis by fibroblasts. By contrast, thealcohols (Exxal® 10, Exxal® 12, and Exxal® 13) from which compound A ofthe present invention is derived, all increased collagen synthesis.

EXAMPLE 2

This example provided carboxymethylation of an alcohol.

Potassium tertiary-butoxide (9.42 g, 0.084 mole) was weighed out into asmall round bottom flask under moisture free atmosphere (N₂ dry box). Tothis was then added 25 ml dry p-dioxane and while stirring, a mixture ofExxal® 13 alcohol (4.0 g, 0.02 mole) and chloroacetic acid (1.89 g, 0.02mole) in 15 ml dry p-dioxane was added. The heterogeneous reactionmixture was then stirred and heated at slight reflux overnight under N₂.The overnight heating caused a slight coloration to the mixture. Heatingwas stopped and after cooling to room temperature the solids werefiltered and washed with p-dioxane and suction dried to give 6.70 glightly colored paste. The paste was dissolved in water and acidifiedwith HCl and extracted with chloroform (separatory funnel). Thechloroform was dried (MgSO₄) and after filtration, removal of chloroform(rotavap) yielded about 0.90 g of light brown oily liquid product. ¹Hand ¹³C NMR's of the liquid product indicated desired carboxymethylatedproduct (acid form) (¹H singlet at 4.11 ppm for R—O—CH₂CO₂ and multipletat 3.56 ppm for R—CH₂—O—) (¹³C peaks at 60.34 and 67.88 ppm for the—CH₂—O—CH₂—CO). This was further supported by GC analysis of the liquidproduct (silylated) versus starting Exxal® 13 alcohol and chloroaceticacid. The carboxymethylated product had retention times of about 2minutes and about 6 minutes longer than the alcohol and chloroaceticacid respectively. Half of the carboxymethylated product in acid formwas converted to the sodium salt in water and recovery of the sodiumsalt form was recovered via freeze-drying. Both the acid form and thesalt form of the carboxymethylated product were used in the examplesthat follow.

EXAMPLE 3

This example provided data on inhibition of sebocyte lipogenesis.

The iso-tridecyl carboxymethylated product (hereinafter “iso-tridecylcarboxymethylate”) and sodium salt thereof were obtained from Example 2.

Secondary cultures of human sebocytes obtained from an adult male weregrown in 48-well tissue culture plates (Costar Corp.; Cambridge, Mass.)or 96-well tissue culture plates (Packard Co.; Meriden, Conn.) untilconfluent. Sebocyte growth medium consisted of Clonetics KeratinocyteBasal Medium (KBM) 5 supplemented with 14 μg/ml bovine pituitaryextract, 0.4 μg/ml hydrocortisone, 5 μg/ml insulin, 10 ng/ml epidermalgrowth factor, 1.2×10⁻¹⁰ M cholera toxin, 100 units/ml penicillin, and100 μg/ml streptomycin. All cultures were incubated at 37° C. in thepresence of 7.5% CO₂. Medium was changed three times per week.

On the day of experimentation, the growth medium was removed and thesebocytes washed three times with sterile Dulbecco's Modified EagleMedium (DMEM; phenol red free). Fresh DMEM was added to each sample(duplicates, triplicates, or quadruplicates depending on the experiment)with 5 μL of test agent solubilized in ethanol or sterile, distilledwater either alone or in the presence of one or 10 μM of retinol.Controls consisted of addition of ethanol alone, retinol alone or phenolred, which has estrogen-like activity and was included as a positivecontrol.

Each plate was returned to the incubator for 20 hours followed by theaddition of ¹⁴C-acetate buffer (5 mM final concentration, 56 mCi/mmolspecific activity). Sebocytes were returned to the incubator for fourhours after which each culture was rinsed three times with phosphatebuffered saline to remove unbound label. Radioactive label remaining inthe sebocytes was harvested and counted using a Beckman scintillationcounter.

The results that were obtained are summarized in Tables 2 and 3.

TABLE 2 Treatment % of Control Control 100.0 28 μM Phenol Red 56.5* 280μM Phenol Red 43.3* 1 μM Iso-tridecyl carboxymethylate 80.0* 10 μMIso-tridecyl carboxymethylate 58.2* 100 μM Iso-tridecyl carboxymethylate1.4* 1 μM Iso-tridecyl carboxymethylate (sodium salt) 81.5* 10 μMIso-tridecyl carboxymethylate (sodium salt) 49.6* 100 μM Iso-tridecylcarboxymethylate (sodium salt) 1.2* *statistically significant at p <0.01

As shown in Table 2, iso-tridecyl carboxymethylate and/or salts thereofenhanced inhibition of lipogenesis at all tested concentrations.

TABLE 3 Treatment % of Control Control 100.0 28 μM Phenol Red 92.0 280μM Phenol Red 61.7* 1 μM Retinol 91.8 10 μM Retinol 105.7 1 μMIso-tridecyl carboxymethylate (sodium salt) 75.8* 1 μM Iso-tridecylcarboxymethylate (sodium salt) + 65.4* 1 μM Retinol 1 μM Iso-tridecylcarboxymethylate (sodium salt) + 65.1* 10 μM Retinol 10 μM Iso-tridecylcarboxymethylate (sodium salt) 66.0* 10 μM Iso-tridecyl carboxymethylate(sodium salt) + 63.2* 1 μM Retinol 10 μM Iso-tridecyl carboxymethylate(sodium salt) + 51.6* 10 μM Retinol *statistically significant at p <0.01

As shown in Table 3, iso-tridecyl carboxymethylate salt, alone or incombination with retinol, improved inhibition of lipogenesis. With theaddition of retinol, however, iso-tridecyl carboxymethylate salt showeda slight increase in the inhibition of lipogenesis.

EXAMPLE 4

This example measured production of procollagen I by fibroblasts inresponse to treatment with various test compounds.

The experiment was conducted as described in Example 1 above. Foldincrease was calculated as a ratio of densitometer reading for cellstreated with a test compound over control. The results that wereobtained are summarized in Table 4:

TABLE 4 Fold Average increase OD Standard Over Test Compound ReadingDeviation Control Control 0.783 0.485 0.001% TGF-b 1.348 0.200 1.72*0.0001% Iso-Tridecyl Carboxymethylate 0.777 0.281 0.99 0.001%Iso-Tridecyl Carboxymethylate 1.295 0.712 1.65* *statisticallysignificant at p < 0.05

As shown in Table 4, iso-tridecyl carboxymethylate increased collagenproduction.

It should be understood that the specific forms of the invention hereinillustrated and described are intended to be representative only.Changes, including but not. limited to those suggested in thisspecification, may be made in the illustrated embodiments withoutdeparting from the clear teachings of the disclosure. Accordingly,reference should be made to the following appended claims in determiningthe full scope of the invention.

What is claimed is:
 1. A skin care cosmetic composition comprising: (i)from about 0.001% to about 50% of a compound of the formula A:R—O—M  (A)  wherein: R is a branched alkyl chain having at least 9carbon atoms, and at least two branches; O is an oxygen atom; and M isselected from the group consisting of (—CH₂CO₂X) and(—(CH₂CH₂O)_(n)—CH₂CO₂X), and mixtures thereof, where n is an integer ofat least 1 and X is hydrogen or a cation; and (ii) a cosmeticallyacceptable vehicle.
 2. The skin care cosmetic composition of claim 1wherein the cation is selected from the group consisting of sodium,lithium, potassium, calcium, magnesium, manganese, and amines.
 3. Theskin care cosmetic composition of claim 1 wherein M is (—CH₂CO₂X) and Xis hydrogen or a cation.
 4. A cosmetic method of reducing or preventingoily skin conditions, the method comprising applying to the skin thecomposition of claim
 1. 5. A cosmetic method of reducing or preventingsebum secretion from sebocytes, the method comprising applying to theskin the composition of claim
 1. 6. A method of stimulating collagensynthesis by fibroblasts in the skin, the method comprising applying tothe skin the composition of claim
 1. 7. A skin care cosmetic compositioncomprising: (i) from about 0.001% to about 50% of a compound of theformula A: R—O—M  (A)  wherein: R is a branched alkyl chain having atleast 9 carbon atoms, and at least two branches; O is an oxygen atom;and M is selected from the group consisting of (—CH₂CO₂X) and(—(CH₂CH₂O)_(n)—CH₂CO₂X) and mixtures thereof, where n is an integer ofat least 1 and X is hydrogen or a cation; and (ii) a retinoid; and (iii)a cosmetically acceptable vehicle.
 8. The skin care cosmetic compositionof claim 7 wherein the cation is selected from the group consisting ofsodium, lithium, potassium, calcium, magnesium, and amines.
 9. The skincare cosmetic composition of claim 7 wherein M is (—CH₂CO₂X) and X ishydrogen or a cation.
 10. A skin care cosmetic composition comprising:(i) from about 0.001% to about 50% of a compound of the formula A:R—O—M  (A)  wherein: R is a branched alkyl chain having 13 carbon atoms,and at least two branches; O is an oxygen atom; and M is selected fromthe group consisting of (—CH₂CO₂X) and (—(CH₂CH₂O)_(n)—CH₂CO₂X), andmixtures thereof, where n is an integer of at least 1 and X is hydrogenor a cation; and (ii) a cosmetically acceptable vehicle.
 11. Thecomposition of claim 10 further comprising a retinoid.